DE1072382B - See heat-stable thermoplastic molding compound from acrylonitrile-containing Polvmerisatgemi - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

kl. 39 b 22/06

INTERNAT. KL. C 08 f

PATENT OFFICE

C O 8 L 33/20

EXPLAINING EDITORIAL 1072 382

B 49098 IVb / 39 b

BOOKING DAY: 3 0 MAY 19 5 8

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL: DECEMB 31, 1959

Polyacrylonitrile, which is spun from solutions, often does not form pure white threads; in addition, the threads yellow in the warmth and through the Exposure to light. Polyacrylonitrile cannot or only insufficiently with the normal dyes to be colored. It is known that you can mitigate these disadvantages if you acrylonitrile with about 2 to 10% of other acrylic or vinyl monomers. z. H. of acrylic or methacrylic acid esters, vinyl acetate. Vinyl propionate. Vinyl pyrrolidone or other basic compounds that can be copolymerized with acrylonitrile, copolymerized. These copolymers can be colored better, but they still have an inadequate whiteness and turn yellow when exposed to heat or prolonged exposure to light

It has now been found that mixtures au> Polyacrylonitrile or copolymers containing predominant amounts of acrylonitrile with copolymers, those made of acrylonitrile. Allyl alcohol and allyl alcohol equimolar amounts of sulfur dioxide order, have a high whiteness and hardly turn yellow when heated.

Films or threads that are produced from solutions of these mixtures are films or Fädeti made of polyacrylonitrile or from the known Superior to copolymers with a predominant proportion of acrylonitrile. Also plates or compacts from Mixtures according to the present invention, which are produced by thermoplastic molding, are only very slightly yellowish.

According to the invention with a copolymer of acrylonitrile, allyl alcohol and sulfur dioxide mixing polyacrylonitrile or copolymers, the predominant amounts of acrylonitrile - preferably 85%> and more - may contain, according to the known processes.

The other mixture component is made of acrylonitrile. Allyl alcohol and allyl alcohol a <juimol: iren quantities Sulfur dioxide can pass through in aqueous suspension or in the absence of solvents Polymerization of acrylonitrile with allyl alcohol in the presence of sulfur dioxide will. Sulfur dioxide is only ever present in the structure of the resulting copolymer the allyl alcohol involved equimolar amounts. The ratio of acrylonitrile to allyl alcohol can be in vary widely, and it is possible. 1 to 99% acrylonitrile and correspondingly 99 to 1%> Polymerize allyl alcohol with the allyl alcohol in equimolar amounts of sulfur dioxide.

The mixtures of pure polyacrylonitrile or a copolymer, the predominant amounts Polyacrylonitrile contains, with a copolymer, heat-stable, thermoplastic

Acrylonitrile-containing molding compound

Polymer mixtures

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Konrad Jost, Lützelsachsen,
has been named as the inventor

from acrylonitrile, allyl alcohol and sulfur dioxide can be obtained by mixing the dry polymer

powder can be produced. It is also possible to mix the components in a suitable solvent to solve. This is particularly advantageous when the polymer mixture is processed from a solution will., e.g. 13. in the manufacture of threads. Farther

it is possible to mix the components of the mixture in the form of their aqueous suspension.

Also the mixing ratio of polyacrylonitrile or a polymer with a predominant proportion of acrylonitrile and the other mixing ratio

The component of acrylonitrile, allyl alcohol and sulfur dioxide can be varied as desired. If the received Polymer mixture is to be spun, it must, however, be composed so that it is in Solvents used in the production of spinning

solutions are suitable. solves.

If you use dimethylformamide or butyrolactone as a solvent for the polymer mixture. thus up to about 40% allyl alcohol can be present in the mixture be included. If you leave the poly-

Merengemischen wants to produce moldings by thermoplastic deformation, the mixing ratio can of the monomers in the individual components of the mixture and also the ratio of the two components of the mixture with each other

can be chosen arbitrarily according to the desired property which the shaped bodies should have.

The parts mentioned in the examples are parts by weight. The viscosities were in an intimate Determined solution of dimethylformamide.

Claims (1)

example 1 800 parts of dry polyacrylonitrile powder, which was prepared in the usual manner in aqueous suspension by polymerizing monomeric acrylonitrile in aqueous solution with redox catalysts, are mixed with 200 parts of a dry, pulverized copolymer which, in aqueous suspension, consists of 163 parts of acrylonitrile, 18 parts of allyl alcohol and 19 Parts of sulfur dioxide was prepared in the presence of 2 parts of potassium persulphate at 40 ° C. and contains 21.5 ^e / o nitrogen, 7.6% oxygen and 4.7% sulfur. The powder mixture with a viscosity η of 2.8 is dissolved in dimethylformamide and mixed with the usual spinning viscosity (falling ball time 80 seconds at 100 ⁰ C) dry or wet-spun. The dissolving and spinning behavior of the mixture does not differ significantly from that of the pure polyacrylonitrile. The strength of the threads lies at 34 to 36 km, i.e. only slightly below the strength of the threads made of pure polyacrylonitrile. The threads are almost pure white, and no yellowing is noticeable ^{after heating at 130 ° C. for one hour.} In terms of whiteness, they are superior to threads made from pure polyacrylonitrile or known acrylonitrile-containing copolymers. Example 2 800 parts of a dry copolymer powder composed of 760 parts of acrylonitrile and 40 parts of methyl acrylate with a viscosity η of 3.15 are mixed with 200 parts of dry powder of the copolymer of acrylonitrile, allyl alcohol and sulfur dioxide used in Example 1 and dry-spun from dimethylformamide solution. The dissolving and spinning behavior of the mixture does not differ significantly from that of the copolymer of acrylonitrile and methyl acrylate. The filaments have a strength from 32 to 34 Rkm, but a copolymer of acrylonitrile and methyl acrylate are almost pure white in contrast to the yellowish threads and are by lstündigem heating at 13O ⁰ C without yellow tinge. Example 3 600 parts of a dry copolymer powder composed of 588 parts of acrylonitrile and 12 parts of acrylic acid amide with a viscosity η of 3.8 are mixed with 400 parts of the same dry powder of the copolymer of acrylonitrile, allyl alcohol and sulfur dioxide used in Example 1 and spun dry or wet from dimethylformamide solution. The viscosity number of the mixture in dimethylformamide is 2.4. The spinning viscosity range is somewhat narrower than that of the copolymer of acrylonitrile and acrylic acid amide. the The strength of the threads obtained is from 27 to 32 Rkm. The threads are pure white even after lstündigem heating to 130 ⁰ C. Example 4 800 parts of a dry copolymer powder made from 768 parts of acrylonitrile and 16 parts of vinylpyrrolidone and 16 parts of N-vinylimidazole, with a ίο relative viscosity of 3,92 are mixed with 200 parts of a copolymer of a dry powder in an aqueous suspension of 64.5 parts of acrylonitrile, 64.5 parts of allyl alcohol and 71 parts of sulfur dioxide in the presence of 1.8 part of potassium persulfate at 30 ⁰ C and has a viscosity number η of 0.28. The powder mixture with a relative viscosity of 2.63 is dissolved in butyrolactone and dry-spun in a known manner. The loosening and spinning behavior is good. The strength of the threads is 26 to 30 Rkm. The threads are pure white, and are not yellowed by virtually lstündigem heating to 130 ⁰ C. Example 5 The polymer mixtures described in Examples 1 to 4 are for 1 hour pre-heated at 150 ° C and then placed in a likewise pre-heated to 150 ⁰ C forms and at a pressure of 200 at the following temperatures for 5 minutes to 4 mm thick plates pressed . Polymer mixture Pressing temperature 180 ⁰ C
175 ° C
160 ⁰ C
150 ⁰ C Appearance clear, yellowish tinge
! clear, weak
Yellow greenish clear, water-light example 1 Example 2 Example 3 Example 4 Moldings made from copolymers of acrylonitrile and produced under the same conditions Methacrylic acid methyl ester or acrylonitrile with such proportions of acrylonitrile as the total of acrylonitrile of the mixtures used in Examples 1 to 4 are in each case yellow-brown. Patent vnspkucii Heat-stable, thermoplastic molding compound, consisting of a mixture of polyacrylonitrile or a copolymer with a predominant proportion of acrylonitrile with a copolymer from acrylonitrile, allyl alcohol and the allyl alcohol equimolar amounts of sulfur dioxide.